CN103608361A

CN103608361A - Method of concentrating an aqueous dispersion comprising organic polymer particles and silicon dioxide particles

Info

Publication number: CN103608361A
Application number: CN201280030551.1A
Authority: CN
Inventors: K.潘斯库斯; R.穆施; D.潘特克; S.基希迈尔
Original assignee: Bayer Pharma AG
Current assignee: Covestro Deutschland AG
Priority date: 2011-06-21
Filing date: 2012-06-20
Publication date: 2014-02-26
Anticipated expiration: 2032-06-20
Also published as: WO2012175553A1; CN103608361B; EP2723775B1; TW201319091A; EP2723775A1; TWI583701B

Abstract

A method of concentrating an aqueous dispersion comprising organic polymer particles and silicon dioxide particles comprising the steps of: a) providing an aqueous dispersion comprising organic polymer particles and silicon dioxide particles, the dispersion having an initial content of organic polymers and an initial content of silicon dioxide, b) contacting the dispersion of step a) with a creaming agent to yield an aqueous serum phase and an aqueous concentrated phase, and c) separating the serum phase from the concentrated phase. The invention further relates to a concentrated aqueous silicon dioxide dispersion which is obtained by a method according to the invention and to the use of such a dispersion as an adhesive.

Description

The method of the concentrated aqueous dispersion that comprises organic polymer particles and silica dioxide granule

The present invention relates to the method for the concentrated aqueous dispersion that comprises organic polymer particles and silica dioxide granule.The invention still further relates to the concentrated silicon-dioxide aqueous dispersion and the purposes of this type of dispersion as tackiness agent that by method of the present invention, obtain.

Silica dispersion and organic polymer dispersion are considered to have many beneficial effects as the combination of adhesive dispersion.Can be by polymerization single polymerization monomer under inorganic particle dispersion exists or by mixing preformed inorganic particle and organic polymer dispersion realizes this combination.

In US 2004/0077761 A1, provide the example of the first situation, it discloses the organic polymer dispersion containing filler.The polymerization under the particle of at least one filler exists of the organic polymer of this dispersion.The granularity of filler particles and the ratio of polymer beads are in the scope of 1.1:1 to 20:1.

In US 2006/0115642 A1, provide the example of latter event, the method and the method for preparing fabric enhancing and fibre-reinforced concrete and other cement base products (comprising the product that those arranged) of the goods finishing fiber product of the aqueous dispersion of using based on sovprene is wherein provided.In strengthening the method for one of concrete and cement, wherein disclosed improvement comprises fiber product is immersed in a kind of goods, and described goods comprise: (a) about 20 aqueous dispersion based on sovprene to about 99 % by weight; (b) about 1 aqeous suspension based on being selected from the inoganic solids of oxide compound, carboxide (carboxides) and silicate to about 80 % by weight; (c) optionally, be selected from the polymeric dispersions of polyacrylic ester, poly-acetic ester, urethane, polyureas, rubber and epoxide, (d) optionally, be selected from additive and the auxiliary of resin, stablizer, antioxidant, linking agent, crosslinking accelerator, filler, thickening material and mycocide, wherein (a) and weight percent (b) add up to 100 % by weight the weight based on non-volatile cut.

During with the silica dispersion being obtained commercially, may there is undesirable dilution of gained mixture, especially with regard to dioxide-containing silica in the adhesive dispersion being obtained commercially when mixing.This necessitates follow-up enrichment step.

The several method that improves the solid content of polymer latex is as known in the art, and described polymer latex is as SBR(styrene butadiene ribber), NBR(acrylonitrile butadiene rubber), the dispersion of sovprene, polyhutadiene, polyisoprene, natural rubber, polyvinyl chloride or (methyl) acrylate dispersoid or its multipolymer.

At Houben-Weyl, volume XIV/1 " Makromolekulare Stoffe " rolls up 1, the 4th edition, in the 515th page (1961), at Polymer Colloids, Elsevier Applied Science Publishers, the 272nd page (1985) or Industrial and Engineering Chemistry, volume 43,1951 February, 406-412 page, the non-limit that provides these class methods in Ernst Schmidt and R. H. Kelsey " Creaming Latex with Ammonium Alginate " is collected.

For example, US 2009/0234064 A1 discloses the elastomerics aqueous dispersion that comprises disperse phase and water.This disperse phase comprises and contains curable aliphatic conjugated diene elastomer, as at least one additive of the elastomerics of polyisoprene and minor amount.This water comprises water and other optional components in solvable state or dispersion state.Can be by elastomerics be dissolved in solvent mixture, then gained solution be changed into aqueous emulsion and prepare elastomerics aqueous dispersion as rubber and additive.By this aqueous emulsion concentrated and therefrom stripping solvent to produce rare latex.By the rare latex reconcentration of gained.The goods of being made by this elastomerics aqueous dispersion comprise medical gloves, condom, probe set, dam, finger-stall, conduit etc. for tooth.

Combination concentrated of the dispersion of inorganic and organic substance wherein do not described.

The method of the dispersion of disclosed concentrated organic substance has following shortcoming: may there is the agglomeration (when adding ionogen, freezing, water evaporation) of the particle of this dispersion, strainer hole may blocked (ultrafiltration) or foaming may hinder effective separation (centrifugal).In the use of creaming agent, the granularity of processed latex is considered to have conclusive significance.Although the natural rubber latex that granularity is 400 nanometers can be without any problems livering fast, by ammonium alginate livering for example granularity be the SBR latex also unsuccessful (Ind. Eng. Chem. 43,407 (1951)) of 78 nanometers.

Therefore wishing can concentrated polymer particle and the dispersion of silica dioxide granule and there is no above-mentioned shortcoming.The object of this invention is to provide such method.

According to the present invention, the method for the concentrated aqueous dispersion that comprises organic polymer particles and silica dioxide granule by comprising following step realizes this purpose:

A) provide the aqueous dispersion that comprises organic polymer particles and silica dioxide granule, described dispersion has the initial content of organic polymer and the initial content of silicon-dioxide;

B) make step dispersion a) contact to produce the concentrated phase of water-based clear liquid phase and water-based with creaming agent,

Described clear liquid has mutually than step a) dispersion in the low organic polymer content of the initial content of organic polymer and/or have than step a) dispersion in the low dioxide-containing silica of initial content of silicon-dioxide, and

Describedly concentrated have than step a mutually) dispersion in the high organic polymer content of the initial content of organic polymer and/or have than step a) dispersion in the high dioxide-containing silica of initial content of silicon-dioxide, and

C) by described clear liquid phase and described concentrated being separated.

Another embodiment of this claimed invention is the method for the concentrated aqueous dispersion that comprises organic polymer particles and silica dioxide granule that comprises following step:

Described clear liquid has mutually than step a) dispersion in the low organic polymer content of the initial content of organic polymer and have than step a) dispersion in the low dioxide-containing silica of initial content of silicon-dioxide, and

Describedly concentrated have than step a mutually) dispersion in the high organic polymer content of the initial content of organic polymer and have than step a) dispersion in the high dioxide-containing silica of initial content of silicon-dioxide, and

C) by described clear liquid phase and described concentrated being separated.

Find surprisingly, method of the present invention can concentrated polymer particle/silica dispersion and there is no particle agglomeration in enrichment step process.The size-grade distribution of this dispersion, particularly with regard to silica dioxide granule, almost constant.

Equally surprisingly, by the selection of creaming agent, the composition of this livering mixture can affected aspect organic and inorganic component.

Before livering, by dispersion of polymer particle, particularly polymer latex adds to and in inorganic dispersant, has improved attainable concentration and realized organic granular and being uniformly distributed of inorganic particle.The granule density of livering mixture is apparently higher than also mixing subsequently by concentrating respectively each component the concentration realizing.

The step of the method a) relates to initial (meaning before the enrichment step) content separately that provides the aqueous dispersion that comprises organic polymer particles and silica dispersion, described dispersion to have above-mentioned particle.Not strict necessity, but in this dispersion, can have the organic substance of organic cosolvent or other dissolving yet, as Oxyranyle emulsifying agent, for example, in the amount based on maximum 20 % by weight of dispersion.

The step b of the method) require this dispersion to contact with creaming agent.This creaming agent can for example provide with the aqueous solution, hydro-colloid or solid form.If need, can also have solubility promoter.

Reported in the literature different livering methods:

Stevens?AH?(1934):?Improvements?Relating?to?the?Treatment?of?Rubber?Latex?B.?P.?415,?133；appl.?23.2.33；publ.?23.8.34

Rhodes?E,?Sekaran?KC?(1937):?Concentration?of?latex.?B.P.474,?651；appl.?24.8.36；publ.?4.11.37.

Dafader?NC,?Haque?ME,?Akhtar?F,?Ahmad?MU,?Utama?MJ?(1996),Macromol.?Sci.,?A?33,?1?(2):?73.

Peethambaran?NR,?Kuriakose?B,?Rajan?M,?Kuriakose?APJ?(2003):?Rheological?behaviour?of?nature?rubber?latex?in?the?presence?of?surface-active?agents；Appl.?Polym.?Sci.,?41(5-6):?975。

The creaming agent that is applicable to the method according to this invention is all creaming agents well known in the prior art, but preferably use multipolymer and bivalent ions salt, for example lime acetate of alginate, derivatived cellulose, methylcellulose gum, agar, poly-(methyl) acrylic acid salt, alkyl (methyl) acrylate and/or vinylbenzene and unsaturated sulfonic acid derivative or the unsaturated monobasic of ethylenic or polycarboxylic acid or its salt.The size of this creaming agent is lower than the polymer particle size as given herein, lower than 10 nanometers.

This creaming agent has the effect that makes this separated dispersion become rich solid water and low solid water phase (clear liquid phase).Therefore, clear liquid (dispersion) solids content in is mutually lower than in the dispersion providing at first, and concentrated (dispersion) solids content in is mutually higher than in the dispersion providing at first.Due to the high-density of inoganic solids, concentrated special formation mutually below phase, clear liquid forms top phase.For example, with regard to absolute value, clear liquid is can have≤25 % by weight mutually, and the solid content of preferably≤20 % by weight.Can be for example by estimating or measuring phase boundary by other optical instrument.

Step c) separation in can be carried out in the settling vessel described in DE 10 145 097 A1.

Described livering can be lower than, be equal to or higher than the discontinuous or continuous method at the temperature of room temperature.The method is preferably in about room temperature, carries out at 10 to 35 ℃.At separating step c) also can wait for the scheduled time before.The described scheduled time can be 24 hours.

The present invention of contact preferred embodiment more detailed description.Unless clearly indicated separately in literary composition, they can independent assortment.

In an embodiment of the method according to this invention, described organic polymer particles is selected from styrene butadiene ribber particle, acrylonitrile butadiene rubber particle, pellets of polychloroprene, chloroprene-dichloroprene copolymer pellet, polyhutadiene particle, polyisoprene particle, chlorination polyisoprene particle, polyurethane particles, natural rubber particle, polyvinyl chloride or (methyl) acrylate particles and/or their copolymer pellet.

This organic polymer particles is polyurethane particles and/or pellets of polychloroprene preferably, as poly--2 chlorobutadiene or poly-(2 chlorobutadiene-2,3-dichloroprene 1,3) multipolymer.Can the letex polymerization in alkaline medium obtain polychloroprene dispersion by chloroprene and ethylenically unsaturated monomers that optionally can copolymerization.In WO 2002/24825 A1, DE 30 02 734 A1 or US 5,773,544, provided example.Particularly preferably be the polychloroprene dispersion of making by successive polymerization, in WO 2002/24825 A1 embodiment 2 and DE 30 02 734 A1 embodiment 6, wherein can between 0.01% to 0.3%, change conditioning agent content.

Can obtain polyurethane dispersions by letex polymerization.At US 20050085584 A1, table 1 dispersion B(is from Bayer Material Science AG, the Dispercoll of Germany ^?u), in or at US 20050131109 A1, in the embodiment in table 1., provided example.

In another embodiment of the process according to the invention, described organic polymer particles exists with the form of polymer latex.In the context of the present invention, polymer latex is understood to be solid polymer particle and is dispersed in the dispersion in liquid phase, and wherein this forms milk sap in water.Preferred polymer latex is to have density>=1.01 g/cm ³, and more preferably>=1.06 g/cm ³those.

In another embodiment of the process according to the invention, in step dispersion a), the initial content of organic polymer is that >=20 % by weight are to≤99 % by weight.Be preferably >=30 % by weight of this initial content are to≤90 % by weight.

In another embodiment of the process according to the invention, the mean particle size of described organic polymer particles is that >=20 nanometers are to≤400 nanometers.Mean particle size also can be known as primary average particle size and can pass through according to H. G. M ü ller, Progr. Colloid Polym. Sci. 107, and the ultracentrifugation of 180-188 (1997) is measured.It is expressed as mass average value (mass average).Preferably using primary average particle size is that >=40 nanometers are to those polymer beads of≤200 nanometers.

In another embodiment of the process according to the invention, this silica dioxide granule exists with the form of silicon sol, silica gel, fumed silica dispersions, precipitated silica dispersion or these mixture.

Silicon sol is the colloidal solution of amorphous silica in water, and it is also known as silicon dioxide gel, but conventionally referred to as silicon sol.Silicon-dioxide is wherein the spheroidal particle form of surface hydroxylation.This colloidal solid typically have a diameter from 1 to 200 nanometer, (by G. N. Sears, Analytical Chemistry rolls up 28, N. 12 to the BET specific surface area associated with these granulometric facies, 1981-1983, the method in December, 1956 is measured) be 15 to 2000 meters squared per gram.This SiO ₂the surface of particle has the electric charge being compensated by corresponding counter ion, to stablize this colloidal solution.The stable silicon sol of alkali conventionally has 7 to 11.5 pH and comprises basifier, for example a small amount of Na ₂o, K ₂o, Li ₂o, ammonia, organic nitrogen(ous) base, tetra-alkyl ammonium hydroxide or basic metal or ammonium aluminate.Silicon sol can be also slightly acidic form, is semistable colloidal solution.In addition, by using Al ₂(OH) ₅cl coated surface, can prepare the silicon sol that positively charged ion is prepared.The solids concn of this silicon sol is generally 5 to 60 % by weight SiO ₂.

The preparation procedure of silicon sol comprises following production stage substantially: by ion-exchange by water glass dealkalize, set and stablize required specific SiO ₂granularity (distribution), set required specific SiO ₂concentration, and if suitably, modification SiO ₂particle surface, for example, use Al ₂(OH) ₅cl, or with silane, as for example set forth in WO 2004/035474.SiO in these steps ₂particle does not keep colloid dissolved state.This has explained and has very effectively served as for example existence of the discrete primary granule of tackiness agent.

Silica gel refer to have from the relatively loose pore texture not waiting to densification, elasticity is to silicon-dioxide solid denseness, that form or do not form colloid.This silicon-dioxide is the poly-silicic acid highly concentrating.There is from the teeth outwards siloxanes and/or silanol.By water glass by preparing silica gel with reacting of mineral acid.Primary particle size is generally 3 to 20 nanometers, and specific surface area is generally 250 to 1000 meters squared per gram (according to DIN 66131).

Further distinguish pyrolytic silicon dioxide and precipitated silica.In the precipitator method, introduce water, then add water glass and acid, as H simultaneously ₂sO ₄.This produces colloid primary granule, and it agglomeration occurs and be grown in together along with reaction is carried out, and forms agglomerate.Its specific surface area is generally 30 to 800 meters squared per gram (DIN 66131) and primary particle size is generally 5 to 100 nanometers.The primary granule of these solid silicas is firmly crosslinked, forms secondary agglomerate.

Can by flame hydrolysis or by arc of lighting legal system for pyrolysis (pyrolysis (fumed)) silicon-dioxide.The main synthesis method of pyrolytic silicon dioxide is flame hydrolysis, wherein in oxyhydrogen flame, decomposes tetrafluorosilane.The silicon-dioxide forming in this method is X-ray amorphous.Pyrolytic silicon dioxide has than the significantly less OH group of precipitated silica on the surface of their almost atresia.The pyrolytic silicon dioxide of making by flame hydrolysis has the specific surface area of 50 to 600 meters squared per gram (DIN 66131) and the primary particle size of common 5 to 50 nanometers conventionally; The silicon-dioxide of making by arc of lighting method has the specific surface area of 25 to 300 meters squared per gram (DIN 66131) and the primary particle size of common 5 to 500 nanometers conventionally.

Synthesizing with the further details of character of silicon-dioxide about solid form is found in for example K. H. B ü chel, H.-H. Moretto, P. Woditsch " Industrielle Anorganische Chemie ", Wiley VCH Verlag 1999, chapters and sections 5.8.

If the SiO existing with separated solid form ₂starting material, if pyrolysis or precipitated silica are for polymeric dispersions of the present invention, it changes into SiO by dispersion ₂aqueous dispersion.

In order to prepare silica dispersion, can use known decollator, be preferably those that are applicable to generation high shear rate, as Ultraturrax or dish-type dissolver.

Preferred silica dispersion is colloidal silica.This SiO ₂particle equally preferably has hydroxyl on particle surface.

In another embodiment of the process according to the invention, in step silicon-dioxide aqueous dispersion a), the initial content of silicon-dioxide is that >=1 % by weight is to≤80 % by weight.Be preferably >=10 % by weight of this initial content are to≤70 % by weight.

In another embodiment of the process according to the invention, in step silicon-dioxide aqueous dispersion a), the mean particle size of silica dioxide granule is that >=1 nanometer is to≤400 nanometers.This mean particle size also can be known as primary average particle size also can be by preferably as H. G. M ü ller, Progr. Colloid Polym. Sci. 107, the ultracentrifugation of setting forth in 180-188 (1997) mensuration.It is expressed as mass average value.Preferably use its SiO ₂the primary average particle size of particle is extremely≤100 nanometers of>=3 nanometers, and particularly preferably>=5 nanometers are to those silicon-dioxide aqueous dispersion of≤70 nanometers.When using precipitated silica, they are ground to reduce granularity.

In another embodiment of the process according to the invention, in step dispersion a), described silica dioxide granule has bimodal or multimodal size-grade distribution.For example, in bimodal situation, a maximum value in size-grade distribution can be in >=5 nanometers in the scope of≤15 nanometers, and another maximum value can be in >=45 nanometers to the scope of≤65 nanometers.Method of the present invention can be prepared the concentrated bimodal or multimodal dispersion that cannot obtain with other method.

In another embodiment of the process according to the invention, creaming agent is selected from alginate, derivatived cellulose, methylcellulose gum, agar, poly-(methyl) acrylate and/or (methyl) alkyl acrylate and/or vinylbenzene and unsaturated sulfonic acid derivative or the unsaturated list of ethylenic-or the multipolymer of poly carboxylic acid or its salt.

Creaming agent is sodiun alginate, potassium alginate and/or ammonium alginate preferably.

In another embodiment of the process according to the invention, described creaming agent provides with aqueous solution form, and the creaming agent content in this aqueous solution is that >=0.5 % by weight is to≤10 % by weight.Preferred concentration is extremely≤5 % by weight of >=1 % by weight, and more preferably >=1.5 % by weight are to≤4 % by weight.

In another embodiment of the process according to the invention, in solid content >=0.2 % by weight based on step dispersion a), the amount to≤10 % by weight exists described creaming agent.Preferred amounts is extremely≤8 % by weight of >=0.3 % by weight, and more preferably >=0.4 % by weight is to≤7 % by weight.

In another embodiment of the process according to the invention, step c) small part that is separated in is undertaken by centrifugal.This greatly accelerates the separation of clear liquid.

The invention still further relates to the concentrated aqueous dispersion that comprises organic polymer particles and silica dioxide granule obtaining by the method according to this invention.About the preferred embodiment of this dispersion, for fear of repetition, with reference to the description about method of the present invention.

The invention still further relates to concentrated aqueous dispersion, wherein comprise >=0.01 % by weight of this aqueous dispersion is to the creaming agent of the residual quantity of≤1 % by weight and >=10 % by weight to the silicon-dioxide of amount of≤60 % by weight and the organic polymer particles (all components adds up to 100 % by weight) of the amount of >=40 % by weight.

" polymer beads " refers to water-fast particle in this application.Term " polymer " dispersion " or " latex " preferably refer to the stable colloidal dispersion of polymer beads in water.The diameter of organic polymer particles is preferably 10 nanometers to 100 micron as described in this article, more preferably 10 nanometers to 1 micron.Preferably, by surface active ingredient, as tensio-active agent or protective colloid or by be incorporated to ionic group (inner emulsifying agent) in polymer backbone, realize the stability of this dispersion.

Polymeric dispersions can directly be synthesized or be synthesized by dispersed polymeres by different polymerizations (as letex polymerization or suspension polymerization) by monomer.Natural rubber from rubber tree (Hevea Brasiliensis) is the example of the polymeric dispersions of natural formation.The dispersion of making according to the method preferably comprises sovprene and/or urethane as organic polymer particles.

According to dispersion of the present invention, can optionally contain other additive and the auxiliary of knowing, for example resin, stablizer, antioxidant, linking agent and crosslinking accelerator from tackiness agent and dispersion technology.For example, can add filler, as silica powder, quartz sand, barite, calcium carbonate, chalk, rhombspar or talcum, optional and linking agent, polyphosphate for example, acrylate as many in Sodium hexametaphosphate 99, naphthene sulfonic acid, ammonium or sodium are together, wherein said filler is preferably with 10 to 60 % by weight, more preferably the amount of 20 to 50 % by weight is added, and linking agent preferably adds with the amount of 0.2 to 0.6 % by weight, and all wt per-cent is all by non-volatile cut.

Preferably can add other suitable auxiliary in the amount of 0.01 to 1 % by weight (by non-volatile cut), organic thickening agent for example, maybe can be by inorganic thickening agent, for example wilkinite preferably adds dispersion (a) or (b) or in whole goods, wherein the thickening effectiveness in said preparation is preferably no more than 1000 mPas in the amount of 0.05 to 5 % by weight (by non-volatile cut).

In order to preserve, also mycocide can be added in composition of the present invention.These preferably use in the amount of 0.02 to 1 % by weight (by non-volatile cut).Suitable mycocide is for example phenol and cresols derivative or tin mineral compound or oxazole derivatives, as TEBUCONAZOL or KETOCONAZOL.

Also can be optionally by tackifying resin, the natural resin of unmodified or modification for example, as rosin ester, hydrocarbon resin or synthetic resins, as phthalic ester resin adds in the component for the preparation of these of composition of the present invention or discrete form (referring to for example " Klebharze " R. Jordan, R. Hinterwaldner, 75-115 page, Hinterwaldner Verlag, Munich, 1994).Softening temperature is preferably higher than 70 ℃, higher than alkyl phenol resin and the terpene phenolic resin dispersion of 110 ℃, is more preferably preferred.

Another aspect of the present invention is that dispersion of the present invention is as the purposes of tackiness agent.These binder compositions show high storage stability, can be by their viscosity adjustment to desired level, they have open hour before high initial adhesion strength (no matter their water-content), bonding part and high thermostability.

Another aspect of the present invention is bonding coat and the substrate that the dispersion of the application of the invention obtains as tackiness agent.This type of substrate comprises that footwear for example, foam block, wooden structures are as furniture and toy, clothing item with for the article of automotive industry, as dashboard decoration foil etc.

With reference to the following example and accompanying drawing, further describe the present invention, but do not wish limited by they.

Embodiment

glossary:

Manutex: sodiun alginate (creaming agent), Monsanto, UK

SiO used ₂dispersion:

starting material:

Polychloroprene dispersion: according to carrying out polymerization in the continuous processing of EP 0 032 977 A1.

Dispersion A:

By measure and Controlling System to having in first reactor of polymerization cascade of same reactor of 7 each 70 liter capacities with constant ratio introducing water (W) and monomer phase (M).Also introduce activator phase (A).Be 25 minutes the mean time in each reactor.Described reactor be equivalent to describe in DE 2 650 714 A1 those (to amount be weight part/100 weight part monomer used).

Monomer phase (M): chloroprene 100.0 weight parts

N-dodecyl mercaptan 0.11 weight part

Thiodiphenylamine 0.005 weight part

Water is to (W): deionized water 115.0 weight parts

Sodium salt 2.6 weight parts of sylvic acid

Potassium hydroxide 1.0 weight parts

The aqueous solution (1%) 0.05 weight part of activator phase (A) formamidine sulfinic acid (formamidinesulfine)

Sodium Persulfate 0.05 weight part

Anthraquinone-2-sulfonic acid sodium salt 0.005 weight part.

This reaction easily starts under the internal temperature of 10 ℃.Heat of polymerization dissipates by exterior cooling and makes polymerization temperature remain on 10 ℃.After 70% conversion of monomer, by adding diethyl oxyamine, stopped reaction.By vapor distillation, from polymkeric substance, remove residual monomer.Obtain strong crystallized product.The solid content of product is 33 % by weight, gel content 0 % by weight, and pH is 13.

Dispersion B:

The method is identical with dispersion A's, but the amount of conditioning agent is increased to 0.03 % by weight, and monomer conversion is increased to 80%, and polymerization temperature is increased to 45 ℃ to obtain the polymkeric substance with high gel content.Obtain the not product of so strong crystallization.The solid content of this product is 38 % by weight, gel content 60 % by weight, and pH is 12.9.

method:

1. the aqueous dispersion of livering organic polymer dispersion and silica dispersion, to measure the optimum quantity of creaming agent:

Carry out livering test to measure the amount of the required creaming agent of the maximum solids concn reach in dispersion.Equipment used is Brookfield LV DV III viscometer, Knick KR301 pH meter and Sartorius 1364 laboratory balances.In addition, as 2% solution [w/w] in deionized water, (fresh preparation the day before yesterday) provides creaming agent Manutex.

Record the pH of this mixture and 8 parts of 100 grams of silica dispersion samples are packed in bottle.In sample, add respectively 10,20,30,40 and 50 gram of 2% creaming agent solution soft mixing.Sample at room temperature stores the range estimation of carrying out sample after 24 hours.

The clear liquid forming above this dispersion with ruler measurement, also records result.Finally pass through with this sample of maximum speed of revolution shake homogenizing, and record again pH.

2. size-grade distribution:

By according to H. G. M ü ller, Progr. Colloid Polym. Sci. 107, the median size that the ultracentrifugation of 180-188 (1997) is measured silica dioxide granule is also expressed as mass average value.

3. solid content:

By by this dispersion dry 16-18 hour at 100 ℃, measure solid content.Sample is being heated after 30 minutes at 850 ℃-1000 ℃, measuring SiO ₂amount as ash oontent.

result:

Embodiment 1-5: the mensuration of the optimum quantity of creaming agent:

Embodiment	1	2	3	4	5
						Polychloroprene dispersion B [g]	50	50	50	50	50
Levasil 50 [g]	50	50	50	50	50
						2% Manutex solution [g]	10	20	30	40	50
Clear liquid height [cm]	4.7	5.9	6.0	5.2	4.9
						Clear liquid outward appearance	Opaque	Transparent	Transparent	Opaque	Opaque

According to these experiments, find that the optimum quantity of creaming agent is described 2% solution of 30 grams of every 100 grams of silicon-dioxide/polychloroprene dispersion.

Other livering embodiment 6-8:

Embodiment	6	7	8
				Levasil 50 [g]	50	50	-
Levasil 300 [g]	-	-	50
				Polychloroprene dispersion A [g]	-	50	50
Polychloroprene dispersion B [g]	50	-	-
				The solid content of mixture [%]	44	41.5	31.5
The optimum quantity of 2% Manutex solution [g]	30	60	80
				The solid content [%] of concentrated phase	60.15	63.4	77
The solid content of dried clear liquid [%] (polymkeric substance, alginate, SiO at 100 ℃ ₂)	5.1	2.4	18.3
				The solid content of the clear liquid after pyrolysis [%] (SiO only ₂)	4.48	1.84	16.8
Organic content in clear liquid [%]	0.62	0.56	1.5

Mix 50 grams of Levasil and 50 grams of polychloroprene dispersion and add 2% Manutex solution.After 24 hours, from concentrating mutually, below gets two samples.(Brookfield, main shaft nr. 3 60/min) also measure dried solid content at 100 ℃ to the viscosity of detection sample.Supernatant liquid phase contains solid (dry at 100 ℃).After pyrolysis, leave solid, contain silicon-dioxide.

Embodiment 9: according to the concentration of creaming agent, and the composition of the dispersion after livering:

Mix 50 grams of Levasil 200A (32%) and 50 grams of polychloroprene dispersion B (38%) and add 2% Manutex solution with the amount of stipulating.After storing gained mixture, measure the concentration (absolute value data) of two components in mutually.The results are summarized in below and be depicted in Fig. 1.

Fig. 1 is presented at the solid content (y-axle) of the lower dispersion mixture of various concentration (x-axle) of the Manutex alginate that provide with %.Solid wire connects the data point of the organic content of top in mutually, and dotted line connects the SiO of top in mutually ₂content.Square represent the organic content of top in mutually, the SiO below trilateral represents in mutually ₂content.As can be seen from the figure, consider SiO ₂content, Manutex(alginate) concentration is higher, and result is better.Organic content improves in phase (clear liquid) up slightly, below in phase (high solid district) maintenance constant.But during we find out that below is mutually, the SiO in high solid district for example ₂significantly improving of content.The chemical constitution of the organic and inorganic part in high solid district becomes 57% organism and 43% inorganics from 68% organism and 32% inorganics.

Embodiment 10 and 11: pass through CENTRIFUGAL ACCELERATING livering process in the situation that directly adding solid paste agent:

Result shows, within centrifugal about 10 minutes, is enough to realize results needed, as below " high solid " mutually in inorganic SiO ₂a large amount with organic polymer dispersion.

Claims

1. concentrate the method for the aqueous dispersion that comprises organic polymer particles and silica dioxide granule, it comprises step:

C) by described clear liquid phase and described concentrated being separated.

2. according to the process of claim 1 wherein that described organic polymer particles is selected from styrene butadiene ribber particle, acrylonitrile butadiene rubber particle, pellets of polychloroprene, chloroprene-dichloroprene copolymer pellet, polyhutadiene particle, polyisoprene particle, chlorination polyisoprene particle, polyurethane particles, natural rubber particle, polyvinyl chloride or (methyl) acrylate particles and/or their copolymer pellet.

3. according to the process of claim 1 wherein that described organic polymer particles exists with the form of polymer latex.

4. according to the process of claim 1 wherein that the initial content of organic polymer is that >=20 % by weight are to≤99 % by weight in step dispersion a).

5. according to the method for claim 1, wherein pass through according to H. G. M ü ller, Progr. Colloid Polym. Sci. 107, the mean particle size of the organic polymer particles that the ultracentrifugation of 180-188 (1997) is measured is for >=20 nanometers are to≤400 nanometers and be expressed as mass average value.

6. according to the process of claim 1 wherein that described silica dioxide granule exists with the form of silicon sol, silica gel, fumed silica dispersions, precipitated silica dispersion or these mixture.

7. according to the process of claim 1 wherein that the initial content of silicon-dioxide is that >=1 weight is to≤80 % by weight in step silicon-dioxide aqueous dispersion a).

8. according to the method for claim 1, wherein in step silicon-dioxide aqueous dispersion a), by according to H. G. M ü ller, Progr. Colloid Polym. Sci. 107, the mean particle size of the silica dioxide granule that the ultracentrifugation of 180-188 (1997) is measured is for >=1 nanometer is to≤400 nanometers and be expressed as mass average value.

9. according to the process of claim 1 wherein that described silica dioxide granule has the size-grade distribution of bimodal or multimodal in step dispersion a).

10. according to the process of claim 1 wherein that described creaming agent is selected from alginate, derivatived cellulose, methylcellulose gum, agar, poly-(methyl) acrylate and/or (methyl) alkyl acrylate and/or vinylbenzene and unsaturated sulfonic acid derivative or the unsaturated list of ethylenic-or the multipolymer of poly carboxylic acid or its salt.

11. according to the process of claim 1 wherein that described creaming agent provides with aqueous solution form, and the creaming agent content in the described aqueous solution is that >=0.5 % by weight is to≤10 % by weight.

12. according to the process of claim 1 wherein that the amount to≤10 % by weight exists described creaming agent with >=0.2 % by weight, the solid content meter based on step dispersion a).

13. according to the process of claim 1 wherein step c) in described in be separated to small part and undertaken by centrifugal.

14. by the concentrated aqueous dispersion that comprises organic polymer particles and silica dioxide granule obtaining according to the one or more method of claim 1 to 13.

15. according to the dispersion of claim 14 purposes as tackiness agent.

16. by using the bonding coat obtaining as tackiness agent according to the dispersion of claim 14.

17. by using according to the dispersion of claim 14 as the bonding substrate of tackiness agent.